CN114539482A - High-adhesion high-hardness photocuring resin and preparation process and preparation device thereof - Google Patents
High-adhesion high-hardness photocuring resin and preparation process and preparation device thereof Download PDFInfo
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- 239000000178 monomer Substances 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000010521 absorption reaction Methods 0.000 claims description 9
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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Abstract
The invention provides a high-adhesion high-hardness photocuring resin, a preparation process and a preparation device thereof, wherein the high-adhesion high-hardness photocuring resin comprises urethane acrylate; the functional organic silicon monomer of nano powder comprises functional double bonds, amino and siloxane groups, and the amino of the organic silicon monomer and the double bonds in the polyurethane acrylate accord with the mechanism of conjugate addition reaction by Michael addition reaction and by utilizing the conjugate addition reaction of a nucleophilic carbanion compound and an electrophilic conjugate system, so that the organic silicon is grafted to the polyurethane acrylate; UV photoinitiator, forming a free radical polymer. The high-adhesion high-hardness light-cured resin, the preparation process and the preparation device thereof can be used for preparing a novel UV light-cured resin with good toughness and high hardness, and after light curing, the novel UV light-cured resin has a proper vitrification temperature, high adhesion, high hardness, high light transmittance and corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of cleaning, and particularly relates to high-adhesion high-hardness photocuring resin, and a preparation process and a preparation device thereof.
Background
UV light curable resins have important key functions in many fields of use, and the quality of the resin determines the decorative effect and the service life of the end product. Currently, most of resins adopted at home and abroad are low-hardness high-toughness resins, and the hardness is generally low. Korea is one of the UV light-cured resin production countries representing the international advanced level, the produced resin has good adhesive force, the hardness can reach the excellent performance index of 3-4H, and the high-end UV light-cured resin in China is mostly imported from Korea and has extremely high production cost. Based on the common knowledge of polymer chemistry, the high hardness of the resin means that the resin has poor toughness and poor adhesion. The improvement of the hardness of the resin inevitably leads to the increase of the glass transition temperature of the resin, the increase of the glass transition temperature leads to the obvious increase of the brittleness of the resin, and the obvious reduction of the adhesive force.
However, currently, most of UV curable resins are polyurethane acrylates, and such resins utilize the high adhesive force of polyurethane and the photosensitive property of acrylic resins, and combine with a UV process, so as to realize rapid curing and decoration of the resins on a substrate, and have the characteristics of high adhesive force and the like. However, since the properties of urethane acrylate resin and applied substrate (e.g., glass) determine that high hardness and high adhesion are contradictory in polymer chemistry, the demand for higher hardness of the end product cannot be achieved.
At present, researchers at home and abroad adopt epoxy acrylate and a precursor material of polyurethane acrylate to carry out copolymerization reaction to prepare the epoxy resin-polyurethane-acrylate ternary functional resin, so that the tensile strength and hardness of a film layer are obviously improved, but the adhesive force and the stain resistance are not obviously improved. On the other hand, researchers have tried to improve the stain resistance and adhesion of resins, and they have made use of the characteristics of strong electronegativity of fluorine atoms, high bond energy, and the like to prepare organofluorine-modified urethane acrylates, which significantly improve the stain resistance of resins, but the hardness of resins has not been improved. Therefore, how to realize the high hardness and the high adhesion of the polyurethane acrylate is an important research subject of the glass screen printing industry, and the scheme adopts a special preparation process and a special preparation device to develop a novel UV light-cured resin with good toughness and high hardness.
Disclosure of Invention
The invention aims to provide a high-adhesion high-hardness light-cured resin, a preparation process and a preparation device thereof, which solve the technical problem of how to prepare a novel UV light-cured resin with good toughness and high hardness.
A high-adhesion and high-hardness light-curable resin comprises
A urethane acrylate;
the functional organic silicon monomer of nano powder comprises functional double bonds, amino and siloxane groups, and the amino of the organic silicon monomer and the double bonds in the polyurethane acrylate accord with the mechanism of conjugate addition reaction by Michael addition reaction and by utilizing the conjugate addition reaction of a nucleophilic negative carbon ion compound and an electrophilic conjugate system, so that the organic silicon is grafted to the polyurethane acrylate to obtain the organic silicon modified polyurethane acrylate;
UV photoinitiator, forming a free radical polymer.
The organic silicon monomer is aminopropyltriethoxysilane, and is obtained by heating amino groups, vinyl groups and trichlorosilane which are active groups, wherein the ratio of the aminopropyltriethoxysilane to the trichlorosilane is 3:3: 1-5: 5: 1.
The mass ratio of the organic silicon monomer is 3%, and the mass ratio of the polyurethane acrylate is 97%.
A preparation process of high-adhesion high-hardness photocuring resin specifically comprises the following steps:
step S1: preparing a functional organic silicon monomer and polyurethane acrylate, wherein the organic silicon monomer is aminopropyltriethoxysilane obtained by reacting substances with active groups of amino, vinyl and trichlorosilane in a ratio of 3:3: 1-5: 5:1 at 50-250 ℃ for 5-12 hours while isolating air;
step S2: through Michael addition reaction, by utilizing the conjugate addition reaction of a nucleophilic carbanion compound and an electrophilic conjugate system, the amino group of an organic silicon monomer and the double bond in the polyurethane acrylate conform to the mechanism of the conjugate addition reaction, and the polyurethane acrylate is subjected to organic silicon modification grafting to form a functional polyester material with siloxane, wherein the polyester material is rich in double bonds and is convenient for photocuring;
step S3: UV light is adopted to initiate free radical polymerization and nucleophilic substitution reaction with hydroxyl on the surface of glass to obtain photocuring resin, siloxane is reacted with the hydroxyl on the surface of the glass to perform condensation reaction, so that the adhesive force of the resin on the surface of the glass is obviously improved, double bonds rich in the resin are rapidly subjected to free radical polymerization under the action of a photoinitiator, and the resin is cured to form a film on the surface of the glass;
step S4: and testing and representing the glass transition temperature, viscosity, hardness and boiling resistance of the prepared composite material, selecting a yellowing-resistant photoinitiator combination matched with the wavelength of a light source, and constructing an internal relation between the light intensity and the dosage of the initiator.
The organic silicon monomer is used for modifying polyurethane acrylate, the modified polyurethane acrylate is called resin after being mixed with the monomer of acrylate, and the resin and the UV photoinitiator are subjected to film pressing reaction on a glass sheet.
In the step S1, the surface of the organosilicon monomer nano powder is functionalized with a treating agent containing a terminal double bond or other active functional groups to obtain a nano powder containing a double bond or other active functional groups, and the active functional groups bonded to the surface of the nano particles are further assembled with a polymer monomer to obtain a polymer-based nano hybrid material, wherein the polymer monomer is a polyacrylate monomer or a polyurethane monomer.
In the step S3, the light intensity is 1KW/m2The temperature is 30 ℃, and the curing time is 200 ms;
the absorption wavelength of TPO-L is 390nm, the absorption wavelength of 184 is 330nm, and the absorption wavelength of ITX is 382 nm; the dosage of the photoinitiator TPO-L is 4 percent, the dosage of 184 is 3 percent, and the dosage of ITX is 0.2 percent; the light intensity is 1KW/m2The processing speed is 0.4m2/s。
In the step S4, when the characteristics are shown, the boiling resistance of the product is tested to be excellent and no bubble phenomenon exists through a boiling test at 100 ℃;
the hardness of the coating is more than or equal to 4H through a hardness test;
the grade 0 of the check index is obtained through the check test and the pasting test, and the falling rate is less than or equal to 2 percent.
A preparation device of high-adhesion high-hardness light-cured resin comprises a preparation platform, a heating system and a light-cured system, wherein the heating system and the light-cured system are arranged on the preparation platform, and a water tank is arranged between the heating system and the light-cured system;
and a blocking structure is also arranged between the water tank and the heating system.
The heating system comprises a protective cylinder and a heating furnace arranged in the protective cylinder, a first sealing cover is arranged above a region between the protective cylinder and the heating furnace, a second sealing cover is arranged at the top end of the heating furnace, a handle is arranged on the second sealing cover, the protective cylinder is connected with a protective gas device, and the protective cylinder and the heating furnace are arranged in the preparation platform;
the photocuring system includes that the lifter plate, the setting that the level set up are in the cylinder, the setting of lifter plate bottom end face are in the rotor plate of lifter plate top, the medial surface of rotor plate is provided with the light source, the lifter plate the cylinder all sets up in the inside cavity of preparation platform, the one end of rotor plate passes through the hinge and articulates the upper end opening border of inside cavity.
The baffle that separates the fender structure and be in including the embedding baffle in the preparation platform, with baffle top detachable connects, the articulated roller that is provided with in top of baffle, and the bottom is provided with the embedding post, the length of roller equals the width of inside cavity, the embedding post sets up the up end of baffle.
Compared with the prior art, the invention has the beneficial effects that:
(1) the scheme provides a block polymer with a combination of a hard segment and a soft segment through research and development, the block polymer has an active functional group so as to be convenient for photo-initiated polymerization, and after photo-curing, the block polymer has a proper glass transition temperature, and has high adhesive force, high hardness, high light transmittance and corrosion resistance, so that the high-hardness and high-adhesive-force composite performance of UV photo-curing resin is realized, the block polymer replaces foreign imported products, and performance surpassing is realized.
(2) The technical scheme realizes excellent technical effects, and the prepared light-cured resin has the highest industrial hardness (9H), has the characteristics of high transparency (90%), good wear resistance (steel wire balls are scraped for more than 100 times), high adhesive force (3M hundred-grid test adhesive tapes are pulled for more than 100 times), no cracking, acid resistance, corrosion resistance and the like;
on the basis of keeping high adhesive force and high transparency of the product, the hardness of the product is improved by 2-5H compared with that of light-cured resin at home and abroad, the scratch resistance is improved by more than 100 times, the durability of a terminal product is obviously improved, the technical barrier at home and abroad is basically broken through, all-round surpassing of the performance is achieved while import substitution is realized, the international leading level is achieved, the industrial competitiveness of China in the fine chemical field is improved, and finally, in the aspect of economic benefit, the corresponding research and development project of the technical scheme can realize the newly increased 6000 million sales income and the profit and tax of 660 ten thousand yuan.
(3) According to the scheme, the advantages of polyurethane, acrylic acid and organic silicon are perfectly combined and fully embodied through a high polymer material modification technology, the photocuring resin has the characteristics of yellowing resistance, aging resistance and the like of the acrylic acid, and simultaneously has the advantages of high tensile strength, temperature change resistance and the like of the polyurethane, and also has the characteristics of high hardness, low surface tension, excellent weather resistance and the like of the organic silicon, so that the problem that the high hardness and high adhesive force of the existing resin cannot coexist is solved, and the technical barrier of the industry is broken through.
(4) The project improves the compatibility of the nano powder with the modified polyurethane acrylate of the organic silicon by modifying the surface of the nano powder, can realize the characteristic of quick curing under mild reaction conditions by a silk-screen front-end polymerization technology, can perfectly overcome the defects of oxidation, agglomeration, interface layer phase separation and the like of the surface of the nano powder caused by overlong reaction time in the traditional preparation method by the two technologies, obviously improves the mechanical property and mechanical property of an organic material, creatively utilizes a silk-screen front-end free radical polymerization method, and quickly realizes the preparation process of the nano powder/polymer composite material.
(5) The scheme provides that the nano powder forms a uniform and thermodynamically stable microstructure in the polymer, so that the internal relation between the macroscopic property and the microstructure of the synthetic material can be further explored, the optimal relation and proportion between the microstructure and the toughness and hardness of the material can be determined, the optimal regulation and control of the toughness and hardness of the composite material can be realized, and finally the nano powder/polymer composite material with high hardness, high transparency and high adhesive force can be obtained.
(6) Set up heating system and photocuring system in this scheme, be provided with the water tank between heating system and photocuring system, can satisfy the heating in whole preparation process, boiling test, illumination solidification procedure, have multi-functional characteristics, furthermore, the fender structure that separates that sets up in this scheme, on the one hand separate heating system and photocuring system, avoid the interact, on the other hand, the baffle is except having the effect of separation, can also utilize the roller to roll the resin and scribble on the glass board, have multi-functional characteristics.
Drawings
FIG. 1 is a view showing an external structure of an apparatus for producing a photocurable resin in the example of the present invention.
FIG. 2 is a view showing the internal structure of an apparatus for producing a photocurable resin in the example of the present invention.
Fig. 3 is a structural view of a baffle in the embodiment of the present invention.
FIG. 4 is a diagram of a manufacturing process of a silk-screen glass product in an embodiment of the present invention.
Wherein, in the figure: 1. preparing a platform; 2. a partition plate; 3. a first sealing cover; 31. a protective cylinder; 4. a shielding gas device; 5. a second sealing cover; 51. heating furnace; 6. a handle; 7. a baffle plate; 71. an embedded column; 8. a cover plate; 81. a water tank; 9. a rotating plate; 91. a lifting plate; 10. a roll shaft; 11. a heating system; 12. a light curing system; 13. a blocking structure.
Detailed Description
In order to make the technical features of the present solution clearer, the present solution is explained by the following embodiments.
A high-adhesion and high-hardness light-curable resin comprises
A urethane acrylate;
the functional organic silicon monomer of nano powder comprises functional double bonds, amino and siloxane groups, and the amino of the organic silicon monomer and the double bonds in the polyurethane acrylate accord with the mechanism of conjugate addition reaction by Michael addition reaction and by utilizing the conjugate addition reaction of a nucleophilic negative carbon ion compound and an electrophilic conjugate system, so that the organic silicon is grafted to the polyurethane acrylate to obtain the organic silicon modified polyurethane acrylate;
UV photoinitiator, forming a free radical polymer.
The organosilicon monomer is aminopropyltriethoxysilane, and is obtained by heating amino, vinyl and trichlorosilane serving as active groups, wherein the ratio of the aminopropyltriethoxysilane to the trichlorosilane is 3:3: 1-5: 5: 1.
The mass ratio of the organic silicon monomer is 3 percent, and the mass ratio of the polyurethane acrylate is 97 percent.
A preparation process of high-adhesion high-hardness photocuring resin specifically comprises the following steps:
step S1: preparing a functional organic silicon monomer and polyurethane acrylate, wherein the organic silicon monomer is prepared by reacting substances with active groups of amino, vinyl and trichlorosilane in a ratio of 3:3: 1-5: 5:1 at 50-250 ℃ for 5-12 hours, and isolating air in the process to obtain aminopropyltriethoxysilane;
step S2: through Michael addition reaction, by utilizing the conjugate addition reaction of a nucleophilic carbanion compound and an electrophilic conjugate system, the amino group of an organic silicon monomer and the double bond in the polyurethane acrylate conform to the mechanism of the conjugate addition reaction, and the polyurethane acrylate is subjected to organic silicon modification grafting to form a functional polyester material with siloxane, wherein the polyester material is rich in double bonds and is convenient for photocuring;
step S3: UV light is adopted to initiate free radical polymerization and nucleophilic substitution reaction with hydroxyl on the surface of glass to obtain photocuring resin, siloxane is reacted with the hydroxyl on the surface of the glass to perform condensation reaction, so that the adhesive force of the resin on the surface of the glass is obviously improved, double bonds rich in the resin are rapidly subjected to free radical polymerization under the action of a photoinitiator, and the resin is cured to form a film on the surface of the glass;
both nucleophilic substitution reactions and condensation reactions are auto-reactions because the species in the resin and the functional groups on the glass have functional groups that are directly reactively bound.
Step S4: and testing and representing the glass transition temperature, viscosity, hardness and boiling resistance of the prepared composite material, selecting a yellowing-resistant photoinitiator combination matched with the wavelength of a light source, and constructing an internal relation between the light intensity and the dosage of the initiator.
The organic silicon monomer is used for modifying polyurethane acrylate, the modified polyurethane acrylate is called resin after being mixed with the monomer of acrylate, and the resin and the UV photoinitiator are subjected to film pressing reaction on a glass sheet.
In step S1, the surface of the organosilicon monomer nanopowder is functionalized with a treating agent containing terminal double bonds or other active functional groups to obtain nanopowder containing double bonds or other active functional groups, and the active functional groups bonded to the surface of the nanoparticles are further assembled with a polymer monomer to obtain a polymer-based hybrid nanopowder, wherein the polymer monomer is a polyacrylate monomer or a polyurethane monomer.
The surface functionalization process means that the silicon monomer is activated by acrylate or substances taking acrylic acid as an active group, so that double bonds or other active functional groups are obtained, and similar dissolving capacity can be provided for subsequent numerical modification.
The reactive functional group self-assembles with the polymer monomer and does not require additional conditions.
In step S3, the light intensity is 1KW/m2The temperature is 30 ℃, and the curing time is 200 ms;
the absorption wavelength of TPO-L is 390nm, the absorption wavelength of 184 is 330nm, and the absorption wavelength of ITX is 382 nm; the dosage of the photoinitiator TPO-L is 4 percent, the dosage of 184 is 3 percent, and the dosage of ITX is 0.2 percent; the light intensity is 1KW/m2The processing speed is 0.4m2/s。
In the step S4, when the characteristics are shown, the boiling resistance of the product is tested to be excellent and no bubble phenomenon exists through a boiling test at 100 ℃;
the hardness of the coating is more than or equal to 4H through a hardness test;
the grade 0 of the check index is obtained through the check test and the pasting test, and the falling rate is less than or equal to 2 percent.
Referring to fig. 1 and 2, the device for preparing the high-adhesion high-hardness light-cured resin comprises a preparation platform 1, a heating system 11 and a light-cured system 12 which are arranged on the preparation platform 1, wherein a water tank 81 is arranged between the heating system 11 and the light-cured system 12, and a cover plate 8 is arranged at the upper end of the water tank 81;
a baffle structure 13 is also provided between the water tank 81 and the heating system 11.
The heating system 11 comprises a protective cylinder 31 and a heating furnace 51 arranged in the protective cylinder 31, a first sealing cover 3 is arranged above a region between the protective cylinder 31 and the heating furnace 51, a second sealing cover 5 is arranged at the top end of the heating furnace 51, a handle 6 is arranged on the second sealing cover 5, the protective cylinder 31 is connected with a protective gas device 4, and the protective cylinder 31 and the heating furnace 51 are arranged in the preparation platform 1;
Referring to fig. 3, keep off structure 13 including embedding baffle 2 in preparation platform 1, with baffle 7 that baffle 2 top detachable is connected, the articulated roller 10 that is provided with in top of baffle 7, and the bottom is provided with embedding post 7, the length of roller 10 equals the width of inside cavity, embedding post 7 sets up the up end at baffle 2.
Glass can be arranged above the lifting plate 91, the glass is flatly placed, the prepared resin composite material is placed on the glass, in order to enable the resin to be uniformly distributed on the surface of the glass, the glass can be preheated, the baffle 7 is detached, and the roll shaft 10 is utilized to roll and coat the resin.
The heating procedure in this embodiment can be performed by using the heating furnace 51 and adjusting the heating furnace 51 to an appropriate temperature, which is described herein.
The specific working process of the invention is as follows:
referring to fig. 4, after the photo-curing resin is prepared, the next step is to prepare a finished silk-screen glass product by using the photo-curing resin, and the specific steps are as follows:
firstly, cutting, toughening and cleaning a glass substrate, and activating the surface of the glass by using a plasma cleaning machine to improve the binding force between the glass and resin;
secondly, adhering resin to the glass by adopting a photocuring imprinting technology, wherein the resin has high viscosity, so that the resin is uniformly distributed on the surface of the glass, and the project adopts the implementation scheme of preheating the glass and roll-coating the resin;
and thirdly, the dispensing amount of the resin is controlled through a microfluidic technology, the resin is imprinted through a PET film, the resin is pre-cured by an LED lamp during the printing process, and patterns on the PET film are formed. Subsequently, the glass attached with the pre-cured resin is deeply cured by a UV furnace (250-400 nm, >50 ℃), and then is softened by a softening furnace (170 ℃, 3-5 min) to further improve the surface drying property of the resin. The improved surface dryness of the resin is beneficial to subsequent printing of the ink, and the resin can react with the ink. And finally, printing and drying the gold bottom, the gray bottom and the frame ink (170 ℃, 10 min) to obtain a finished silk-screen glass product.
The technical features of the present invention which are not described in the above embodiments may be implemented by or using the prior art, and are not described herein again, of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, modifications, additions or substitutions which may be made by those skilled in the art within the spirit and scope of the present invention should also fall within the protection scope of the present invention.
Claims (10)
1. A high-adhesion high-hardness light-cured resin is characterized by comprising
A urethane acrylate;
the functional organic silicon monomer of nano powder comprises functional double bonds, amino and siloxane groups, and the amino of the organic silicon monomer and the double bonds in the polyurethane acrylate accord with the mechanism of conjugate addition reaction by Michael addition reaction and by utilizing the conjugate addition reaction of a nucleophilic negative carbon ion compound and an electrophilic conjugate system, so that the organic silicon is grafted to the polyurethane acrylate to obtain the organic silicon modified polyurethane acrylate;
UV photoinitiator, forming a free radical polymer.
2. The high-adhesion high-hardness photocuring resin as claimed in claim 1, wherein the organosilicon monomer is aminopropyltriethoxysilane, and the active groups are amino, vinyl and trichlorosilane, and the ratio of the aminopropyltriethoxysilane to the trichlorosilane is 3:3: 1-5: 5: 1.
3. The high-adhesion high-hardness photocurable resin according to claim 2, wherein the silicone monomer is present in an amount of 3% by mass, and the urethane acrylate is present in an amount of 97% by mass.
4. A preparation process of high-adhesion high-hardness photocuring resin is characterized by comprising the following steps:
step S1: preparing a functional organic silicon monomer and polyurethane acrylate, wherein the organic silicon monomer is aminopropyltriethoxysilane obtained by reacting substances with active groups of amino, vinyl and trichlorosilane in a ratio of 3:3: 1-5: 5:1 at 50-250 ℃ for 5-12 hours while isolating air;
step S2: through Michael addition reaction, by utilizing the conjugate addition reaction of a nucleophilic carbanion compound and an electrophilic conjugate system, the amino group of an organic silicon monomer and the double bond in the polyurethane acrylate conform to the mechanism of the conjugate addition reaction, and the polyurethane acrylate is subjected to organic silicon modification grafting to form a functional polyester material with siloxane, wherein the polyester material is rich in double bonds and is convenient for photocuring;
step S3: adopting UV light to initiate free radical polymerization and nucleophilic substitution reaction with glass surface hydroxyl to obtain photocuring resin;
step S4: and testing and representing the glass transition temperature, viscosity, hardness and boiling resistance of the prepared composite material, selecting a yellowing-resistant photoinitiator combination matched with the wavelength of a light source, and constructing an internal relation between the light intensity and the dosage of the initiator.
5. The process of claim 4, wherein in step S1, the surface of the organosilicon monomer nanopowder is functionalized with a treating agent containing terminal double bonds or other active functional groups to obtain nanopowders containing double bonds or other active functional groups, and the active functional groups bonded to the surface of the nanoparticles are further assembled with a polymer monomer to obtain a polymer-based hybrid nanomaterial, wherein the polymer monomer is a polyacrylate monomer or a polyurethane monomer.
6. The process according to claim 5, wherein in step S3, the light intensity is 1KW/m2The temperature is 30 ℃, and the curing time is 200 ms;
the absorption wavelength of TPO-L is 390nm, the absorption wavelength of 184 is 330nm, and the absorption wavelength of ITX is 382 nm; the dosage of the photoinitiator TPO-L is 4 percent184 is 3%, and ITX is 0.2%; the light intensity is 1KW/m2The processing speed is 0.4m2/s。
7. The process for preparing high adhesion and high hardness photocurable resin according to claim 6, wherein in step S4, the product is tested to have excellent boiling resistance and no bubble phenomenon by the boiling test at 100 ℃ during characterization;
the hardness of the coating is more than or equal to 4H through a hardness test;
the grade 0 of the check index is obtained through the check test and the pasting test, and the falling rate is less than or equal to 2 percent.
8. The device for preparing the high-adhesion and high-hardness light-cured resin is characterized by comprising a preparation platform (1), a heating system (11) and a light-curing system (12), wherein the heating system (11) and the light-curing system (12) are arranged on the preparation platform (1), and a water tank (81) is arranged between the heating system and the light-curing system;
and a blocking structure (13) is also arranged between the water tank (81) and the heating system (11).
9. The apparatus for preparing high adhesion and high hardness photocurable resin according to claim 8, wherein the heating system (11) comprises a protective cylinder (31), a heating furnace (51) disposed in the protective cylinder (31), a first cover (3) is disposed above the region between the protective cylinder (31) and the heating furnace (51), a second cover (5) is disposed on the top end of the heating furnace (51), a handle (6) is disposed on the second cover (5), the protective cylinder (31) is connected with a shielding gas device (4), and the protective cylinder (31) and the heating furnace (51) are disposed inside the preparation platform (1);
light-cured system (12) are in including lifter plate (91), the setting that the level set up lifter plate (91) bottom face the cylinder, set up rotor plate (9) of lifter plate (91) top, the medial surface of rotor plate (9) is provided with the light source, lifter plate (91) the cylinder all sets up in the inside cavity of preparation platform (1), the hinge is passed through to the one end of rotor plate (9) articulates the upper end opening border of inside cavity.
10. The apparatus for preparing high adhesion and high hardness photocurable resin according to claim 9, wherein the barrier structure (13) comprises a partition (2) embedded in the preparation platform (1), a baffle (7) detachably connected to the top end of the partition (2), the top end of the baffle (7) is hinged to a roller (10), the bottom end of the baffle is provided with an embedded column (71), the length of the roller (10) is equal to the width of the internal cavity, and the embedded column (71) is arranged on the upper end surface of the partition (2).
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